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WO2018044128A1 - Électrolyte polymère et batterie secondaire au lithium le comprenant - Google Patents

Électrolyte polymère et batterie secondaire au lithium le comprenant Download PDF

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Publication number
WO2018044128A1
WO2018044128A1 PCT/KR2017/009621 KR2017009621W WO2018044128A1 WO 2018044128 A1 WO2018044128 A1 WO 2018044128A1 KR 2017009621 W KR2017009621 W KR 2017009621W WO 2018044128 A1 WO2018044128 A1 WO 2018044128A1
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Prior art keywords
formula
group
polymer electrolyte
integer
lithium
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English (en)
Korean (ko)
Inventor
안경호
박솔지
이정훈
이철행
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LG Chem Ltd
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LG Chem Ltd
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Priority to US16/080,094 priority Critical patent/US10700379B2/en
Priority to EP17847053.0A priority patent/EP3407415B1/fr
Priority to CN201780016221.XA priority patent/CN108780921B/zh
Priority claimed from KR1020170112015A external-priority patent/KR102070381B1/ko
Publication of WO2018044128A1 publication Critical patent/WO2018044128A1/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a polymer electrolyte having improved ion conductivity and a lithium secondary battery including the same.
  • the lithium secondary battery includes a positive electrode and a negative electrode including an electrode active material capable of inserting / releasing lithium ions, a separator interposed therebetween, and an electrolyte as a transfer medium of lithium ions.
  • electrolytes are liquid electrolytes in which lithium salts are dissolved in organic solvents, and have a high risk of leakage, fire, and explosion, and are capable of growing dendrite, which may cause self-discharge and heating of lithium batteries.
  • Such a polymer electrolyte is known to be suitable for lithium batteries for electric vehicles, large storage batteries, etc., since there is no risk of ignition as compared with the case of using a liquid electrolyte.
  • an electrolyte including a polyethylene oxide or a polyether having an ion dissociation ability in a main chain is proposed.
  • these polymer electrolytes have a disadvantage that they have low ion conductivity and oxidation stability of 4.0V or less at room temperature and low temperature.
  • the polymer electrolyte is used in combination with other conductive materials, there is a disadvantage in that it causes non-uniformity of ion transfer on the electrode surface due to different Li ion migration water.
  • the present invention has been made to solve such a problem.
  • the first technical problem to be solved by the present invention is to provide a polymer electrolyte with improved ion conductivity.
  • the second technical problem to be solved by the present invention is to provide a lithium secondary battery with improved electrochemical stability and lifespan by including the polymer electrolyte of the present invention.
  • R 1 and R 2 are each independently an alkylene group having 1 to 4 carbon atoms unsubstituted or substituted with fluorine,
  • n, n and o are each the number of repeating units
  • n is an integer of any one of 1 to 10,
  • n is an integer of any one of 1 to 10,
  • o is an integer of any one of 1 to 500.
  • the weight ratio of the copolymer: lithium salt represented by Formula 1 may be 7: 3 to 9.5: 0.5.
  • copolymer represented by Formula 1 may be at least one selected from the group consisting of compounds represented by Formula 1a to Formula 1c.
  • n is an integer of any one of 1 to 10,
  • n is an integer of any one of 1 to 10,
  • o is an integer of any one of 1 to 500.
  • the copolymer represented by Formula 1 may be a copolymer represented by Formula 2 below.
  • R ' 1 and R' 2 are each independently an alkylene group having 1 to 4 carbon atoms unsubstituted or substituted with fluorine,
  • R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms
  • R 4 is an alkylene group having 1 to 6 carbon atoms
  • R 5 is an alkylene group having 1 to 5 carbon atoms, or -CO-NH-R 6 -NH-CO-O-,
  • R 6 is an aliphatic, alicyclic or aromatic hydrocarbon group
  • n1 and o1 are each the number of repeating units
  • n 1 to 10
  • n1 is an integer of any one of 1 to 10,
  • o1 is an integer of any one of 1-500.
  • the aliphatic hydrocarbon group is an alkylene group having 1 to 20 carbon atoms; C1-C20 alkylene group containing an isocyanate group (NCO); An alkoxylene group having 1 to 20 carbon atoms; Alkenylene groups having 2 to 20 carbon atoms; Or an alkynylene group having 2 to 20 carbon atoms, wherein the alicyclic hydrocarbon group is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms; A substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms containing an isocyanate group (NCO); A cycloalkenylene group having 4 to 20 carbon atoms; Or a heterocycloalkylene group having 2 to 20 carbon atoms, wherein the aromatic hydrocarbon group is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or a heteroarylene group having 2 to 20 carbon atoms.
  • NCO
  • the copolymer represented by Formula 2 may be at least one selected from the group consisting of copolymers represented by Formulas 2a to 2c.
  • n2, o2 are each repeating unit numbers
  • n2 is an integer of any one of 1 to 10,
  • n2 is an integer of any one of 1 to 10,
  • o2 is an integer of any one of 1-500.
  • n3, n3, and o3 are each the number of repeat units
  • n3 is an integer of any one of 1 to 10,
  • n3 is an integer of any one of 1 to 10,
  • o3 is an integer of any one of 1-500.
  • n4 and o4 are each repeating unit number
  • n4 is an integer of any one of 1 to 10,
  • n4 is an integer of any one of 1 to 10,
  • o4 is an integer of any one of 1-500.
  • the weight average molecular weight (Mw) of the copolymer represented by Formula 2 may be 200 g / mol to 100,000 g / mol.
  • polymer electrolyte of the present invention may further include a ceramic electrolyte.
  • the ceramic electrolyte may be a phosphate-based electrolyte selected from the group consisting of lithium phosphate, lithium titanium phosphate, lithium aluminum titanium phosphate, and lithium aluminum germanium phosphate; Sulfide-based electrolytes selected from the group consisting of SiS 2 (Li x Si y S z ) -based glasses, P 2 S 5 (Li x P y S z ) -based glasses, lithium germanium thiophosphate and lithium phosphorus sulfide-based glass; Lithium lanthanum titanate; Lithium nitride; Lithium lanthanum zirconate; And tantalum pentoxide may include a single substance or a mixture of two or more selected from the group consisting of.
  • the weight ratio of the copolymer represented by Chemical Formula 2 to the ceramic electrolyte may be 1: 0.1 to 1: 9.
  • polymer electrolyte of the present invention may further include inorganic particles.
  • the inorganic particles are Al 2 O 3 , BaTiO 3 , SnO 2 , CeO 2 , SiO 2 , TiO 2 , Li 3 PO 4 , NiO, ZnO, MgO, Mg (OH) 2 , CaO, ZrO 2 , Y 2 O 3 , Pb (Zr, Ti) O 3 , Pb 1 - x La x Zr 1 - y Ti y O 3 (PLZT, where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), PB (Mg 3 Nb 2 / 3 ) O 3 -PbTiO 3 and hafnia may include a single or a mixture of two or more selected from the group consisting of.
  • the weight ratio of the copolymer represented by Formula 2 to the inorganic particles may be 1: 0.1 to 1: 7.0.
  • the polymer electrolyte of the present invention may further include a plasticizer.
  • the plasticizer may include at least one or more compounds of a carbonate compound, a lactone compound, an alkyl ether compound, an alkyl acetate compound, and an alkyl propionate compound, wherein the copolymer represented by Chemical Formula 2:
  • the weight ratio of may be 1: 0.1 to 1: 0.5.
  • the polymer electrolyte provides a lithium secondary battery including the polymer electrolyte of the present invention.
  • the polymer electrolyte may be disposed on at least one surface of the positive electrode and the negative electrode.
  • the lithium secondary battery may include a separator, wherein the polymer electrolyte may be disposed on at least one surface of at least one of the positive electrode, the negative electrode, and the separator.
  • a copolymer containing a fluorine-substituted or unsubstituted polyalkylene ether repeating unit can be prepared a polymer electrolyte that implements a high ion conductivity, and further comprising, thereby improving the electrochemical stability and life characteristics
  • a lithium secondary battery can be manufactured.
  • FIG. 1 to 3 schematically show various configuration examples of a secondary battery including a polymer electrolyte according to an embodiment of the present invention.
  • a "repeating unit” means the unit derived from the monomer formed by superposing
  • the repeating unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
  • R 1 and R 2 are each independently an alkylene group having 1 to 4 carbon atoms unsubstituted or substituted with fluorine,
  • n, n and o are each the number of repeating units
  • n is an integer of any one of 1 to 10,
  • n is an integer of any one of 1 to 10,
  • o is an integer of any one of 1 to 500.
  • R 1 and R 2 are alkylene groups having 1 to 4 carbon atoms substituted with fluorine.
  • n, m, and o respectively refer to the number of repetitions (the number of recurring units), and the repeating units n, m, and o each have a predetermined rule or do not have a rule. And can be arranged alternately, in graft form or randomly.
  • the lithium salt is a component included to further improve the effect of lithium cation transfer characteristics, specifically, Li + as a cation, and F ⁇ , as an anion.
  • the lithium salt is at least any one selected from the group consisting of LiPF 6 , LiBF 4 , LiClO 4 , LiN (CF 3 SO 2 ) 2 , LiN (FSO 2 ) 2 , and LiN (CF 3 SO 2 ) 2 . It may include one or more.
  • the lithium salt may be included in the polymer electrolyte 5M or less, in order to obtain the optimum anti-corrosion film formation effect of the electrode surface, more specifically, the copolymer represented by the formula (1): lithium salt is 7: 3 to 9.5: 0.5 It may be included in the weight ratio. At this time, when the content ratio of the lithium salt is less than 0.5, the Li ion concentration is insufficient, the resistance may be increased and at the same time a heterogeneous reaction in the negative electrode may be caused. If the content ratio of lithium salt exceeds 3, the possibility of precipitation above the concentration capable of dissociating lithium salt increases.
  • the copolymer represented by Chemical Formula 1 may include a copolymer represented by Chemical Formulas 1a to 1c as a representative example.
  • n, n and o are each the number of repeating units
  • n is an integer of any one of 1 to 10,
  • n is an integer of any one of 1 to 10,
  • o is an integer of any one of 1 to 500.
  • the copolymer represented by the formula (1) may be a copolymer represented by the following formula (2).
  • R ' 1 and R' 2 are each independently an alkylene group having 1 to 4 carbon atoms unsubstituted or substituted with fluorine,
  • R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms
  • R 4 is an alkylene group having 1 to 6 carbon atoms
  • R 5 is an alkylene group having 1 to 5 carbon atoms, or -CO-NH-R 6 -NH-CO-O-,
  • R 6 is an aliphatic, alicyclic or aromatic hydrocarbon group
  • n1, o1 are each the number of repeat units
  • n 1 to 10
  • n1 is an integer of any one of 1 to 10,
  • o1 is an integer of any one of 1-500.
  • the aliphatic hydrocarbon group is an alkylene group having 1 to 20 carbon atoms; C1-C20 alkylene group containing an isocyanate group (NCO); An alkoxylene group having 1 to 20 carbon atoms; Alkenylene groups having 2 to 20 carbon atoms; Or an alkynylene group having 2 to 20 carbon atoms;
  • the alicyclic hydrocarbon group is a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms; A substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms containing an isocyanate group (NCO); A cycloalkenylene group having 4 to 20 carbon atoms; Or a heterocycloalkylene group having 2 to 20 carbon atoms,
  • the aromatic hydrocarbon group is substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or a heteroarylene group having 2 to 20 carbon atoms.
  • copolymer represented by Formula 2 may be at least one selected from the group consisting of copolymers represented by the following Formulas 2a to 2c.
  • n2, o2 are each repeating unit numbers
  • n2 is an integer of any one of 1 to 10,
  • n2 is an integer of any one of 1 to 10,
  • o2 is an integer of any one of 1-500.
  • n3, n3, and o3 are each the number of repeat units
  • n3 is an integer of any one of 1 to 10,
  • n3 is an integer of any one of 1 to 10,
  • o3 is an integer of any one of 1-500.
  • n4 and o4 are each repeating unit number
  • n4 is an integer of any one of 1 to 10,
  • n4 is an integer of any one of 1 to 10,
  • o4 is an integer of any one of 1-500.
  • the weight average molecular weight (Mw) of the copolymer represented by Formula 2 may be about 200 g / mol to 100,000 g / mol, specifically 200 g / mol to 70,000 g / mol, the weight average molecular weight of the copolymer Within the above range, mechanical properties, processability (formability), and electrochemical stability can be ensured.
  • m, n and o can be appropriately changed according to the weight average molecular weight of the copolymer within the above range.
  • the weight average molecular weight may be measured using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the GPC measurement system alliance 4 instrument is stabilized. Once the instrument is stabilized, inject the standard sample and the sample sample into the instrument to obtain a chromatogram and calculate the molecular weight according to the analytical method (System: Alliance 4, Column: Ultrahydrogel linear x 2, eluent: 0.1M NaNO 3 (pH 7.0) phosphate buffer, flow rate: 0.1 mL / min, temp: 40 °C, injection: 100 ⁇ L)
  • the copolymer represented by the formula (1) constituting the polymer electrolyte of the present invention is an incombustible compound, and is a polymer having low vapor pressure and thermal, chemical and oxidative stability.
  • the copolymer including the fluorine-substituted or unsubstituted polyalkylene ether repeating unit represented by Formula 1 includes an anionic fixed phase such as F - or O - in the structure, side reactions and salts of lithium cations (Li + ) It is possible to suppress decomposition of (salt) and the like, thereby improving the transfer effect and stability of lithium ions. Furthermore, in the case of the fluorinated structure, since the electrostatic properties of the polymer backbone are increased by high electronegativity, there is an effect of stabilizing or fixing the negative ions of the electrolyte.
  • the interfacial resistance can be reduced and a polymer electrolyte capable of ensuring high ion conductivity can be produced.
  • polymer electrolyte of the present invention may be prepared in the form of a composite further comprising a ceramic electrolyte in order to secure mechanical properties and to improve room temperature and low temperature conductivity.
  • the ceramic electrolyte examples include lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 ), lithium aluminum titanium phosphate (Li x Al y Ti z (PO 4 ) 3 ); LATP), and a phosphate-based electrolyte selected from the group consisting of lithium aluminum germanium phosphate (Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 ; LAGP); Sulfide-based electrolytes selected from the group consisting of SiS 2 (Li x Si y S z ) -based glasses, P 2 S 5 (Li x P y S z ) -based glasses, lithium germanium thiophosphate and lithium phosphorus sulfide-based glass; Lithium lanthanum titanate (Li 0.5 La 0.5 TiO 3 ; LLTO); Lithium nitride (Li x N y ); Lithium lanthanum zirconate (Li
  • the amount of the copolymer is preferably higher than that of the ceramic electrolyte in order to reduce the interfacial resistance or increase the flexibility of the polymer electrolyte membrane.
  • the weight ratio of the copolymer represented by Chemical Formula 2 to the ceramic electrolyte may be appropriately changed according to the degree of curvature of the electrode surface and the driving temperature of the cell, more specifically 1: 0.1 to 1: 9, more specifically 1: 0.1 to 1: 6.
  • the weight ratio of the ceramic electrolyte exceeds 9 of the copolymer represented by Formula 2, it is difficult to form the polymer electrolyte composite. Furthermore, in order to effectively improve the electrode and the interfacial resistance increase, it is more preferable that the content of the ceramic electrolyte is included in 6 weight ratio or less compared to the copolymer represented by the formula (2). If the ceramic electrolyte content is less than 0.1 weight ratio compared to the copolymer represented by Formula 2, the effect of improving room temperature and low temperature conductivity is low.
  • polymer electrolyte of the present invention may be prepared in the form of a composite further including inorganic particles in order to secure mechanical properties and to improve electrochemical stability.
  • the inorganic particles may be Al 2 O 3 , BaTiO 3 , SnO 2 , CeO 2 , SiO 2 , TiO 2 , Li 3 PO 4 , NiO, ZnO, MgO, Mg (OH) 2 , CaO, ZrO 2 , Y 2 O 3, Pb (Zr, Ti) O 3 (PZT), Pb 1- x La x Zr 1-y Ti y O 3 (PLZT, where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), PB (Mg 3 Nb 2/3 ) O 3 -PbTiO 3 (PMN-PT) and hafnia (HfO 2 ) single or a mixture of two or more selected.
  • the weight ratio of the copolymer represented by Formula 2 to the inorganic particles may be 1: 0.1 to 1: 7.0, specifically 1: 0.2 to 1: 7.0. If the weight ratio of the inorganic particles exceeds 7.0 compared to the copolymer represented by Formula 2, not only is it difficult to form a polymer electrolyte but also needs an additional electrolyte capable of filling the pores due to pores generated in the membrane.
  • the polymer electrolyte may further include a binder to implement the dispersibility of the particles or the effect of increasing the strength of the film.
  • the binder may be a conventional binder used in electrode production, and non-limiting examples thereof include polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), teflon or mixtures thereof. .
  • PVDF polyvinylidene fluoride
  • SBR styrene-butadiene rubber
  • teflon teflon or mixtures thereof.
  • the binder may be included in a small amount, specifically, the weight ratio of the copolymer represented by the formula (2): binder may be 1: 0.1 to 1: 0.5. If the weight ratio of the binder exceeds 0.5 compared to the copolymer represented by Formula 2, the resistance may increase, and thus a disadvantage may occur in that the ion conductivity is greatly reduced.
  • the polymer electrolyte of the present invention may further include a plasticizer to implement an effect of enhancing ion transfer characteristics.
  • the plasticizer may include at least one compound of a carbonate compound, a lactone compound, an alkyl ether compound, an alkyl acetate compound, and an alkyl propionate compound.
  • the carbonate-based compound may include a single material selected from the group consisting of cyclic carbonates and linear carbonates or a mixture of two or more thereof, and may specifically include a cyclic carbonate.
  • Examples of the cyclic carbonate include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), fluoroethylene carbonate (FEC), and the like.
  • Examples of the linear carbonate include diethyl carbonate (DEC) and dimethyl carbonate. (DMC), dipropyl carbonate (DPC), ethylmethyl carbonate (EMC), methyl propyl carbonate (MPC), and the like.
  • the lactone compound may include gamma butyrolactone
  • the ether solvent may include a glyce.
  • the alkyl ether compound may include at least one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, and ethylpropyl ether.
  • the alkyl acetate-based compound may include at least one selected from the group consisting of methyl acetate, ethyl acetate and propyl acetate.
  • the alkyl propionate compound may include at least one selected from the group consisting of methyl propionate, ethyl propionate, propyl propionate, and butyl propionate.
  • the plasticizer may be included in 10% by weight to 50% by weight based on the total weight of the polymer electrolyte.
  • the ion conductivity of the polymer electrolyte of the present invention may be 2.0 ⁇ 10 ⁇ 4 S / cm or more at 25 ° C.
  • it may be at least 4.0 ⁇ 10 ⁇ 4 S / cm at 25 ° C., for example at least 7.5 ⁇ 10 ⁇ 4 S / cm at 25 ° C.
  • the total resistance of the polymer electrolyte may be 0 to 200 k ⁇ .
  • the ion conductivity can be measured in the frequency band 100MHz to 0.1Hz using an AC impedance measurement method according to temperature, using a VMP3 measuring equipment and 4294A.
  • the polymer electrolyte provides a lithium secondary battery comprising the polymer electrolyte of the present invention.
  • the polymer electrolyte is a free-standing polymer electrolyte and may serve as a membrane in the form of a membrane film instead of a general separator.
  • the lithium secondary battery of the present invention may further include a separator as necessary.
  • the polymer electrolyte is prepared in the form of a film and then interposed (introduced) on at least one surface of the prepared negative electrode, the positive electrode and the separator, or the lithium salt and the copolymer represented by Chemical Formula 1 in the organic solvent.
  • the coating solution may be directly applied to at least one surface of the prepared negative electrode, the positive electrode and the separator, and then introduced by drying and curing.
  • the curing can be carried out by heat or light irradiation.
  • the thickness of the polymer electrolyte is preferably a thin membrane in consideration of ion conductivity, but may be about 0.5 ⁇ m to 300 ⁇ m. When the thickness of the electrolyte membrane is 0.5 ⁇ m or more, the strength of the membrane can be secured. If the thickness of the electrolyte membrane is 300 ⁇ m or less, protons (H + ), etc., which are ion transporters, are easily passed, thereby preventing an increase in volume per unit performance of the secondary battery stack. A high performance secondary battery can be manufactured.
  • the positive electrode and the negative electrode constituting the lithium secondary battery of the present invention can be manufactured and used in a conventional manner.
  • the positive electrode may be manufactured by forming a positive electrode mixture layer on a positive electrode current collector.
  • the cathode mixture layer may be formed by coating a cathode slurry including a cathode active material, a binder, a conductive material, a solvent, and the like on a cathode current collector, followed by drying and rolling.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • the positive electrode current collector may be formed of stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. Surface treated with nickel, titanium, silver, or the like may be used.
  • the positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and may specifically include a lithium composite metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel or aluminum. have. More specifically, the lithium composite metal oxide is a lithium-manganese oxide (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxide (eg, LiCoO 2, etc.), lithium-nickel oxide (for example, LiNiO 2 and the like), lithium-nickel-manganese-based oxide (for example, LiNi 1-Y Mn Y O 2 (where, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 ( here, 0 ⁇ Z ⁇ 2) and the like), lithium-nickel-cobalt oxide (e.g., LiNi 1-Y1 Co Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1) and the like), lithium-manganese-cobal
  • the lithium composite metal oxide may be LiCoO 2 , LiMnO 2 , LiNiO 2 , lithium nickel manganese cobalt oxide (eg, Li (Ni 1/3 Mn 1/3 Co 1) in that the capacity characteristics and stability of the battery may be improved. / 3) O 2, Li ( Ni 0.6 Mn 0.2 Co 0.2) O 2, Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2 , Li (Ni 0.7 Mn 0.15 Co 0.15 ) O 2, and Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 , or the like, or lithium nickel cobalt aluminum oxide (eg, Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2 , and the like.
  • the cathode active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of solids in the cathode slurry.
  • the binder is a component that assists in bonding the active material and the conductive material to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of solids in the positive electrode slurry.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, Polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
  • the conductive material is typically added in an amount of 1% to 30% by weight based on the total weight of solids in the positive electrode slurry.
  • Such a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • Specific examples of commercially available conductive materials include Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, Ketjenblack, and EC, which are acetylene black series. (Armak Company), Vulcan XC-72 (manufactured by Cabot Company), and Super P (manufactured by Timcal).
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that becomes a desirable viscosity when including the positive electrode active material and optionally a binder and a conductive material.
  • NMP N-methyl-2-pyrrolidone
  • the concentration of the solids in the positive electrode active material and, optionally, the slurry including the binder and the conductive material may be 40 wt% to 60 wt%, preferably 40 wt% to 50 wt%.
  • the negative electrode may be prepared by forming a negative electrode mixture layer on the negative electrode current collector.
  • the negative electrode mixture layer may be formed by coating a negative electrode slurry including a negative electrode active material, a binder, a conductive material, a solvent, and the like on a negative electrode current collector, followed by drying and rolling.
  • the negative electrode current collector generally has a thickness of 3 to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like on the surface, aluminum-cadmium alloy and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the negative electrode active material is lithium-containing titanium composite oxide (LTO); Carbon-based materials such as hardly graphitized carbon and graphite carbon; Li x Fe 2 O 3 (0 ⁇ x ⁇ 1), Li x2 WO 2 (0 ⁇ x2 ⁇ 1), Sn x3 Me 1 -x3 Me ' y3 O z (Me: Mn, Fe, Pb, Ge; Me' Metal complex oxides such as Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen, 0 ⁇ x3 ⁇ 1; 1 ⁇ y3 ⁇ 3; 1 ⁇ z3 ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O
  • the negative active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of solids in the negative electrode slurry.
  • the binder is a component that assists the bonding between the conductive material, the active material and the current collector, and is typically added in an amount of 1 to 30 wt% based on the total weight of solids in the negative electrode slurry.
  • binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, poly Propylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • the conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added in an amount of 1 to 20 wt% based on the total weight of solids in the negative electrode slurry.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the solvent may include an organic solvent such as water or NMP, alcohol, etc., and may be used in an amount that becomes a desirable viscosity when including the negative electrode active material and optionally a binder and a conductive material.
  • concentration of the solids in the slurry including the negative electrode active material and, optionally, the binder and the conductive material may be 50 wt% to 75 wt%, preferably 50 wt% to 65 wt%.
  • a separator is selectively introduced between the anode and the cathode.
  • the separator serves to block internal short circuits of both electrodes and to impregnate an electrolyte, to prepare a separator composition by mixing a polymer resin, a filler, and a solvent, and then directly coating and separating the separator composition on an electrode to separate the separator film.
  • the separator film separated from the support may be formed by laminating on the electrode.
  • the said polymer resin is not specifically limited, For example, Olefin type polymers, such as a chemical resistance and hydrophobic polypropylene; A composite porous separator in which an inorganic material is added to the porous separator substrate; Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
  • Olefin type polymers such as a chemical resistance and hydrophobic polypropylene
  • a composite porous separator in which an inorganic material is added to the porous separator substrate Sheets or non-woven fabrics made of glass fibers or polyethylene are used.
  • the pore diameter of the porous separator is generally 0.01 to 50 ⁇ m, porosity may be 5 to 95%.
  • the thickness of the porous separator may generally range from 5 to 300 ⁇ m.
  • a polymer electrolyte is disposed on at least one surface of at least one of the anode and the cathode, or at least one surface of at least one of the cathode, the cathode and the separator.
  • the polymer electrolyte is prepared by dissolving a lithium salt and a copolymer represented by Chemical Formula 1 in a solvent to prepare a coating solution, and then coating the coating solution on at least one surface of the prepared negative electrode, the positive electrode and the separator, and then drying the prepared solution.
  • the film may be prepared in the form of a film using a lithium salt and the copolymer represented by Chemical Formula 1, and then interposed (introduced) on at least one surface of the prepared negative electrode, the positive electrode, and the separator.
  • the solvent may include, as the main solvent, an organic solvent such as N-methylpyrrolidone (NMP; N-methyl pyrroridone), acetone, dimethylacetamide, or dimethylformaldehyde, an inorganic solvent such as water, or a mixture thereof.
  • NMP N-methylpyrrolidone
  • acetone dimethylacetamide
  • dimethylformaldehyde dimethylformaldehyde
  • an inorganic solvent such as water, or a mixture thereof.
  • FIGS. 1 to 3 examples of various configurations of a lithium secondary battery including a polymer electrolyte according to an embodiment of the present invention are schematically illustrated in FIGS. 1 to 3, but are not limited thereto.
  • the lithium secondary battery of the present invention includes a polymer electrolyte 13 positioned at an interface between the negative electrode 11 and the porous separator 15, and a positive electrode 17 disposed on the other side of the separator. Include.
  • the lithium secondary battery of the present invention is a polymer electrolyte 23 located at the interface between the positive electrode 27 and the porous separator 25, disposed on the other side of the separator And a cathode 21.
  • the lithium secondary battery of the present invention has a polymer electrolyte 33 positioned at an interface between the positive electrode 37 and the negative electrode 31 instead of the separator, and the other surface of the negative electrode. It includes a polymer electrolyte 33 disposed in.
  • the lithium secondary battery of the present invention is manufactured as an electrode assembly by winding or folding the negative electrode, the positive electrode, the polymer electrolyte of the present invention, and optionally the separator in a conventional manner as described in Figures 1 to 3 above. can do.
  • the lithium secondary battery according to an embodiment of the present invention may be manufactured by accommodating and sealing the electrode assembly in a case.
  • a secondary battery is manufactured including only a solid electrolyte layer without an additional solvent.
  • the characteristics of the solid electrolyte layer itself should be excellent.
  • the ionic conductivity is inferior to that of the liquid electrolyte, various problems may occur in the practical application of the battery using the solid electrolyte.
  • the present invention by forming a thickness of the polymer electrolyte to the level of 0.5 ⁇ m to 300 ⁇ m, it is possible to ensure the same level of conductivity as the separator in which the current electrolyte is impregnated, and in the case of some composite type electrolyte Additional conductivity improvements and increased Li freedom allow for superior performance over electrolytes. In particular, even if the conductivity at room temperature is lowered, the ion conductivity at high temperature can be minimized. Therefore, life and safety in a high temperature battery can be ensured.
  • a certain level of liquid electrolyte may be additionally injected into the case.
  • the liquid electrolyte includes an electrolyte salt and a non-aqueous organic solvent.
  • lithium salts used as the electrolyte salt is delivered for a conventional electrochemical device, salt, (i) Li +, Na +, K + cations and (ii) selected from the group consisting of PF 6 -, BF 4 -, Cl - , Br -, I -, ClO 4 -, AsF 6 -, CH 3 CO 2 -, CF 3 SO 3 -, N (CF 3 SO 2) 2 -, C (CF 2 SO 2) 3 - from the group consisting of It can consist of a combination of selected anions.
  • the electrolyte salt may be included in the concentration of 1M to 2M in the electrolyte.
  • non-aqueous organic solvent is not particularly limited as long as it is a conventionally usable organic solvent.
  • examples thereof include a cyclic carbonate compound, a linear carbonate compound, an alkyl ether compound, an alkyl acetate compound, an alkyl propionate compound, And a second organic solvent including at least one compound of nitrile compounds.
  • the cyclic carbonate-based compound may include at least one selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and fluoroethylene carbonate (FEC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • FEC fluoroethylene carbonate
  • the linear carbonate compound is at least selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate It may include one or more.
  • the alkyl ether compound may include at least one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, and ethylpropyl ether.
  • the alkyl acetate-based compound may include at least one selected from the group consisting of methyl acetate, ethyl acetate and propyl acetate.
  • the alkyl propionate compound may include at least one selected from the group consisting of methyl propionate, ethyl propionate, propyl propionate, and butyl propionate.
  • the nitrile compound is acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile And at least one selected from the group consisting of difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, and 4-fluorophenylacetonitrile.
  • the cyclic carbonate compounds are high viscosity organic solvents and can be preferably used because they have high dielectric constants and dissociate lithium salts in the electrolyte.
  • a low viscosity, low dielectric constant linear carbonate such as cyclic carbonate and ethyl methyl carbonate, dimethyl carbonate or diethyl carbonate
  • an electrolyte having high electrical conductivity may be used, and thus it may be more preferably used.
  • the anode mixture slurry was applied to an aluminum (Al) thin film having a thickness of 20 ⁇ m so as to have a thickness of 10 ⁇ m, and dried to prepare a cathode 27.
  • a cathode 21 was prepared by coating 20 ⁇ m Li metal on a 20 ⁇ m thick copper foil.
  • an electrode assembly is manufactured through a polyolefin-based separator (thickness: 20 ⁇ m) 25 between the prepared anode and the cathode including a polymer electrolyte, and the electrode assembly is placed in a pouch-type battery case.
  • LiCoO 2 as cathode active material 92 wt%, 4 wt% carbon black as the conductive material and 4 wt% PVDF as the binder component were added to N-methyl-2 pyrrolidone (NMP) as a solvent to prepare a positive electrode slurry.
  • NMP N-methyl-2 pyrrolidone
  • the anode mixture slurry was applied to an aluminum thin film having a thickness of 20 ⁇ m so as to have a thickness of 10 ⁇ m, and dried to prepare a cathode 17.
  • a negative electrode 11 was prepared by coating 20 ⁇ m Li metal on a 20 ⁇ m thick copper foil.
  • an electrode assembly is manufactured through a polyolefin-based separator (thickness: 20 ⁇ m) 15 between the prepared cathode and the anode including a polymer electrolyte, and the electrode assembly is placed in a pouch-type battery case.
  • a battery was manufactured in the same manner as in Example 2, except that Al 2 O 3 was used instead of lithium lanthanum zirconate (LLZO) when preparing the polymer electrolyte in Example 2.
  • LLZO lithium lanthanum zirconate
  • the cathode mixture was applied to an aluminum (Al) thin film having a thickness of 20 ⁇ m so as to have a thickness of 10 ⁇ m, and dried to prepare a cathode 37.
  • a negative electrode 31 was prepared by coating 20 ⁇ m Li metal on a 20 ⁇ m thick copper foil.
  • an electrode assembly was prepared by stacking a negative electrode and a positive electrode including the prepared polymer electrolyte without a polyolefin-based separator, and storing the electrode assembly in a pouch-type battery case.
  • EC / DEC 5: 5
  • An electrolyte solution containing 1M LiFSI mixed with the solution was injected to prepare a 4.2V full cell.
  • a battery was manufactured in the same manner as in Example 1, except that the copolymer represented by Chemical Formula 2b was used instead of the copolymer of Chemical Formula 2a when preparing the polymer electrolyte in Example 1.
  • a battery was manufactured in the same manner as in Example 1, except that the polymer electrolyte was prepared in Example 1, instead of the copolymer of Formula 2a, instead of the copolymer of Formula 2a.
  • a battery was manufactured in the same manner as in Example 1, except for adding a plasticizer (FEC) to the preparation of the polymer electrolyte in Example 1.
  • FEC plasticizer
  • a battery was manufactured in the same manner as in Example 1, except for including the copolymer represented by Formula 3 in place of the copolymer of Formula 2a in Example 1.
  • a battery was manufactured in the same manner as in Example 1, except that the copolymer represented by Formula 4 was used instead of the copolymer of Formula 2a in Example 1.
  • the ion conductivity of the polymer electrolyte of Example 1 consisting of the copolymer represented by the formula (2a) is 3.0 ⁇ 10 -4
  • the ion conductivity of the polymer electrolyte of Examples 5 and 6 consisting of the copolymer represented by the formulas (2b) and (2c) It is superior to 2.5 ⁇ 10 -4 and 1.2 ⁇ 10 -4 .
  • the ion conductivity of the polymer electrolyte of Examples 2 and 3 further comprising a ceramic electrolyte was 6.8 ⁇ 10 ⁇ 4 and The ion conductivity of the polymer electrolyte of Example 4, which is 4.0 ⁇ 10 ⁇ 4 and further includes a binder, is 5.2 ⁇ 10 ⁇ 4, which shows that the ion conductivity of the polymer electrolyte of Example 1 is significantly improved.
  • a secondary battery of Reference Example 1 was prepared in the same manner as in Example 1 except that the polymer electrolyte was not included.
  • the lithium secondary batteries of Examples 1 to 7 and the lithium secondary batteries of Comparative Examples 1 and 2 were cycled at a charge and discharge rate of 0.2 C (4.2 V) /0.7 C (3.0 V) at 25 ° C. to charge them. , The discharge capacity was measured, and the results are shown in Table 2 below.
  • the secondary battery of Reference Example 1 had a remaining capacity (%) of 5 after 100 cycles, whereas the secondary batteries of Examples 1 to 7 including the polymer electrolyte of the present invention had 100 cycles. After the remaining capacity is about 40% or more it can be seen that all excellent.

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Abstract

La présente invention concerne : un électrolyte polymère comprenant un sel de lithium, et un copolymère qui comprend une unité de répétition d'éther de polyalkylène substitué ou non substitué ; et une batterie secondaire au lithium le comprenant.
PCT/KR2017/009621 2016-09-02 2017-09-01 Électrolyte polymère et batterie secondaire au lithium le comprenant Ceased WO2018044128A1 (fr)

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US16/080,094 US10700379B2 (en) 2016-09-02 2017-09-01 Polymer electrolyte and lithium secondary battery including the same
EP17847053.0A EP3407415B1 (fr) 2016-09-02 2017-09-01 Électrolyte polymère et batterie secondaire au lithium le comprenant
CN201780016221.XA CN108780921B (zh) 2016-09-02 2017-09-01 聚合物电解质和包括该聚合物电解质的锂二次电池

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